Organosilicon compounds having polyoxyalkylene radicals

ABSTRACT

Organosilicon compounds contain both cationic quat groups and polyoxyalkylene polyether groups prepared by an efficient process which can utilize commercially available starting materials. The polyether groups are not linked to siloxane moieties by quat linking groups, but rather by amine or ammonium groups. The polyester groups may also serve as linking groups between organosilicon moieties.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] This invention relates to organosilicon compounds whereincationic quat groups and polyether groups are attached to a siloxanebody via an amino or ammonium group, and to processes for preparingthem.

[0003] 2. Background Art

[0004] Ternary polysiloxane systems consisting of polysiloxane units,polyether groups and cationic quat groups are of particular interest foruse as textile softeners. However, the syntheses described areexclusively very time-intensive, multi-step processes, since thereactants used are often not available in industry and have to beexplicitly prepared. The associated poor space-time yields renderexisting synthetic processes uneconomical and impracticable.

[0005] Known ternary polysiloxane systems of the kind mentioned abovecan be divided into 4 different classes: A) strictly comb type modifiedsiloxane polymers wherein a polyether group acts as a linking memberbetween the siloxane scaffold and the cationic quat group, or viceversa, i.e., wherein the cationic quat group acts as a linking memberbetween the siloxane scaffold and the polyether group, are described forexample in U.S. Pat. No. 6,030,675; B) linear siloxane copolymers havingterminal cationic quat groups and polyether groups, wherein thepolyether group may also be a linking member to a further siloxane blockhaving a terminal quat group, are described for example in EP 1000959 A;C) polymers wherein the cationic quat groups constitute a bridgingelement between 2 siloxane blocks of the polymer, wherein additionalpolyether groups may be present as 2-valent linking members in thepolymer main chain, or the siloxane scaffold or the cationic quat groupis comb type polyether-modified, are described for example in WO02/10257 A1; D) polysiloxanes which have been terminally and/orlaterally modified with mutually independent polyether groups andcationic quat groups are described for example in U.S. Pat. No.6,313,256 A.

SUMMARY OF THE INVENTION

[0006] The subject invention pertains to organosilicon compoundscontaining both cationic quat groups and polyoxyalkylene polyethergroups prepared by an efficient process which can utilize commerciallyavailable starting materials. The polyether groups are not linked tosiloxane moieties by quat linking groups, but rather by amine orammonium groups. The polyether groups may also serve as linking groupsbetween organosilicon moieties.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

[0007] The invention provides copolymers (Q) of the general formula (I)

A-B-(D-B)_(o)-A  (I),

[0008] where

[0009] A is an —R¹ or —OR¹ radical or a monovalent radical of thegeneral formula (II),

—R—[(NH_(a)E_(b)F_(c))^((a+2b+c−1)+)—R]_(g)—(NH_(d)E_(e)F_(f))^((d+2e+f−2)+)[g(a+2b+c−1)+d+2e+f−2]X⁻  (II),

[0010] R¹ is a hydrogen atom or a monovalent hydrocarbyl radical having1 to 100 carbon atoms that may optionally be interrupted or substitutedby the atoms N, O, P, B, Si, S, or contain —C(O)—, —C(O)O—, —C(O)NR⁹—,—NR⁹—, —O—, —S—, ═N—, ≡N units, or be substituted by —NR⁹—, —OH, or —SHgroups,

[0011] R is a divalent hydrocarbyl radical having 1 to 50 carbon atomsthat may optionally be interrupted or substituted by the atoms N, O, P,B, Si, S, or contain —C(O)—, —C(O)O—, —C(O)NR⁹—, —NR⁹—, —O—, —S—, ═N—units,

[0012] R⁹ is a hydrogen atom or a monovalent hydrocarbyl radical having1 to 18 carbon atoms that may optionally be interrupted by the atoms N,O, P, B, Si, S, or substituted by —OH, or —SH groups,

[0013] a, b and c are integers from 0 to 2 subject to the condition thatthe sum total of a+b+c is 1 or 2,

[0014] d, e and f are integers from 0 to 3 subject to the condition thatthe sum total of d+e+f is 2 or 3,

[0015] g is an integer from 0 to 10,

[0016] E is a radical of the general formula (III)

—R²—NR³⁺ ₃  (III),

[0017] R² is a divalent hydrocarbyl radical having 1 to 10 carbon atomsthat may optionally be interrupted or substituted by the atoms N, O, P,B, Si, S, or contain —C(O)—, —C(O)O—, —C(O)NR⁹—, —NR⁹—, —O—, —S—, ═N—,≡N units, or be substituted by —NR⁹—, —OH, —SH groups,

[0018] R³ is a monovalent hydrocarbyl radical having 1 to 20 carbonatoms that may optionally be interrupted or substituted by the atoms N,O, P, B, Si, S or contain —C(O)—, —C(O)O—, —C(O)NR⁹—, —NR⁹—, —O—, —S—,═N—, ≡N units, or be substituted by —NR⁹—, —OH, —SH groups,

[0019] X⁻is an organic or inorganic anion,

[0020] F is a radical of the general formulae (IV) or (V)

—CH₂—CHR⁴—C(O)—G—(R²—G)_(h)—[CH₂CH₂O]_(i)—[C₃H₆O]_(j)—[(CH₂)₄O]_(k)—(R²—G)_(h)—R⁵  (IV),

—CH₂—CH(OH)—CH₂—G—(R²—G)_(h)—[CH₂CH₂O]_(i)—[C3H₆O]_(j)—[(CH₂)₄O]_(k)—(R²—G)_(h)—R⁵  (V),

[0021] R⁴ is a hydrogen atom or methyl radical,

[0022] R⁵ is a hydrogen atom, a monovalent branched or unbranchedhydrocarbyl radical having 1 to 10 carbon atoms or a unit selected fromthe group consisting of CH₂═CR⁴—C(O)—, (R¹)₂N—CH₂—CHR⁴—C(O)—,R⁴—CH₂—C(O)—, HO—CH₂—CH(OH)—CH₂— and

[0023] G is a divalent group —O or —NR⁹—,

[0024] h is 0 or 1,

[0025] i, j and k are each an integer from 0 to 200,

[0026] B is a divalent radical constructed from units which are selectedfrom the general formulae (VIa), (VIb), (VIc), (VId) and A

(SiR⁶ ₂O_(2/2))₁ (VIa), (SiR⁶R⁷O_(2/2))_(m)  (VIb),

(—SiR⁶ ₂—)_(p+1) (VIc), (SiO_(3/2))_(p)  (VId),

[0027] R⁶ is a hydrogen atom, —OR¹, or a monovalent alkyl radical having1 to 200 carbon atoms which may be substituted by halogen atoms,carboxyl groups, epoxy groups, hydroxyl groups or polyether groups andmay optionally be interrupted by the units —C(O)—, —C(O)O—, —C(O)NR⁹—,—NR⁹—, —O—, —S—,

[0028] R⁷ is a monovalent radical of the general formula (II),

[0029] l and m are an integer from 0 to 5000,

[0030] p is an integer from 0 to 500,

[0031] D is a divalent radical of the general formula (VIII),

—{[R—(NH_(a)E_(b)F_(c))]_(n)—J—[(NH_(a)E_(b)F_(c))—R]_(n)}—^([2n(a+2b+c)−4]+[)2n(a+2b+c)−4]X⁻  (VIII),

[0032] n is an integer from 1 to 10,

[0033] J is a divalent radical of the general formulae (IX) or (X),

—CH₂—CHR⁴—C(O)—G—(R²—G)_(h)—[CH₂CH₂O]_(i)—[C₃H₆O]_(j)—[(CH₂)₄O]_(k)—(R²—G)_(h)—C(O)—CHR⁴—CH₂—  (IX),

—CH₂—CH(OH)—CH₂—G—(R²—G)_(h)—[CH₂CH₂O]_(i)—[C₃H₆O]_(j)—[(CH₂)₄O]_(k)—(R²—G)_(h)CH₂—CH(OH)—CH₂—  (X),

[0034] o is an integer≧0,

[0035] with the proviso that the copolymers of the general formula (I)contain at least one E radical and one F radical.

[0036] In contrast to known structures, the cationic quat group and thepolyether group are bonded to the siloxane body via an amino or ammoniumgroup in the copolymers (Q). The quat group does- not act as a bridge,whereas the polyether radical can function as a linking member between 2aminosiloxane bodies.

[0037] The copolymers (Q) are simple to construct in a one-pot process.The syntheses proceed almost quantitatively and because of goodspace-time yields, are more economical than prior processes leading toother structures. In addition, all raw materials are commerciallyavailable in large amounts and do not require additional cost andinconvenience for synthesis. The resulting copolymers (Q) can berendered water soluble or self-emulsifying (so-called “self-emulsifyingsystems”), depending on the stoichiometry chosen, i.e., requiring nofurther auxiliaries for emulsification. The copolymers (Q) can be usedfor treating textile sheet materials, textile fibers and leather, asadditives in coatings and paints, as ingredients in cosmeticformulations and as surface-active agents. They have, in particular,outstanding properties when used as textile softeners properties, whichare superior to those of ordinary amino glycol oils.

[0038] The copolymers (Q) are linear or branched aminopolysiloxaneswhose α, ω and/or lateral amino groups have been modified not only withpolyether groups but also with cationic quat groups. The amino groupsmay optionally be present as quaternary ammonium groups. The numberaverage molecular weight M_(n) of the copolymers (Q) is preferably atleast 500 g/mol, more preferably at least 1000 g/mol, preferably at most1,000,000 g/mol, and more preferably at most 500,000 g/mol. Theviscosity of the copolymers (Q) is preferably in the range fromminimally 10 mm²/s, more preferably minimally 15 mm²/s, to solid at 25°C.

[0039] The amine number of the copolymers (Q) is preferably at least0.001, more preferably at least 0.01, and preferably at most 9, morepreferably at most 6. The amine number identifies the number of ml of 1Normal HCl which are necessary to neutralize 1 g of copolymer.

[0040] In preferable copolymers, a, b and c are 0 or 1; the sum total ofa+b+c is 1; d, e and f are 0, 1 or 2; the sum total of d+e+f is 2 andthe sum total of a+b+c+d+e+f is ≦5, especially 3 or 4; g is at most 5,more preferably, 0 or 1; h is 0; i, j and k are each at most 100 andmore preferably at most 50; 1 and m are at most 1000 and more preferablyat most 500; p is at most 100 and more preferably at most 20; n is atmost 5, more preferably, 1 or 2, most preferably 1; and o is at most1000 and more preferably at most 100.

[0041] Preferably, R is a divalent hydrocarbyl radical having 1 to 10carbon atoms which may optionally be interrupted by N and/or 0 atoms. Ris more preferably a radical independently selected from the formulae—CH₂—, —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₂—NH—(CH₂)₃—, and most preferably aradical from the formulae —(CH₂)—, —(CH₂)₂— and —(CH₂)₃—.

[0042] Preferably, R¹ is a hydrogen atom, a saturated or unsaturatedalkyl radical having 1 to 10 carbon atoms, or a radical of the formulae—C(O)H, —C(O)CH₃, —C(O)CH₂—CH₃ and —CH₂—CH₂—C(O)—O—CH₂—CH₃. Particularpreference is given to hydrogen, methyl, ethyl, propyl, cyclohexyl andacetyl.

[0043] Preferably, R² is independently selected from an uninterrupteddivalent hydrocarbyl radical having 1 to 8 carbon atoms and the radical—CH₂—CH(OH)—CH₂—. Preferred examples of R² are linear or branchedalkylene radicals such as the ethylene, propylene, butylene radical,arylene radicals such as the phenylene radical and the radical—CH₂—CH(OH)—CH₂—.

[0044] Preferably, R³ is an uninterrupted monovalent alkyl radical.Particular preference is given to methyl, ethyl, propyl, butyl,cyclohexyl, dodecyl and octadecyl.

[0045] Preferably, R⁴ is a hydrogen atom.

[0046] Preferably, R⁵ is a hydrogen atom, a saturated or unsaturatedalkyl radical having 1 to 5 carbon atoms or one of the radicals

[0047] —C(O)CH₃, CH₂═CH—C(O)—, (R¹)₂N—CH₂—CH₂—C(O)— and

[0048] Particular preference is given to hydrogen, methyl, ethyl, butyl,acetyl, acryloyl and

[0049] Examples of R⁶ are alkyl radicals such as the methyl, ethyl,n-propyl, isopropyl, 1-n-butyl, 2-n-butyl, isobutyl, tert-butyl,n-pentyl, isopentyl, neopentyl, and tert-pentyl radicals; hexyl radicalssuch as the n-hexyl radical; heptyl radicals such as the n-heptylradical; octyl radicals such as the n-octyl radical and isooctylradicals such as the 2,2,4-trimethylpentyl radical; nonyl radicals suchas the n-nonyl radicals; decyl radicals such as the n-decyl radical;dodecyl radicals such as the n-dodecyl radical; octadecyl radicals suchas the n-octadecyl radical; cycloalkyl radicals such as the cyclopentyl,cyclohexyl, cycloheptyl and methylcyclohexyl radicals; alkenyl radicalssuch as the vinyl, allyl, 3-butenyl, 5-hexenyl, 1-propenyl and1-pentenyl radicals; alkynyl radicals such as the ethynyl, propargyl and1-propynyl radicals; aryl radicals such as the phenyl, naphthyl, anthryland phenanthryl radicals; alkaryl radicals such as the o-, m-, p-tolylradicals, xylyl radicals and ethylphenyl radicals; and aralkyl radicalssuch as the benzyl, phenylethyl and phenylnonyl radicals, or the methoxyor ethoxy radicals.

[0050] Examples of substituted R⁶ radicals are haloalkyl radicals suchas 3,3,3-trifluoro-n-propyl radical, 2,2,2,2′,2′,2′-hexafluoroisopropylradical, and heptafluoroisopropyl radical, and haloaryl radicals such aso-, m- and p-chlorophenyl radicals, or alkyl radicals substituted bycarboxyl, epoxy, hydroxyl or polyether groups. Preferably, R⁶ is ahydrogen atom or a monovalent alkyl radical having 1 to 10 carbon atoms.Methyl is particularly preferred.

[0051] Examples of the radical R⁷ are

[0052] —CH₂—{N[—CH₂—CH(OH)—CH₂—NMe₃]F}⁺ Cl⁻,

[0053] —CH₂—{N[—CH₂—CH(OH)—CH₂—NMe₃]₂F}³⁺ 3 Cl⁻,

[0054] —(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]F}⁺ Cl⁻,

[0055] —(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]₂F}³ ⁺ 3 Cl⁻,

[0056] —(CH₂)₃—NH—(CH₂)₂—{N[—CH₂—CH(OH)—CH₂—NMe₃]F}⁺ Cl⁻,

[0057] —(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH2)₂—NHF}⁺ Cl⁻,

[0058] —(CH₂)₃—NF—(CH₂)₂—{NH[—CH₂—CH(OH)—CH₂—NMe₃]}⁺ Cl⁻,

[0059] —(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₂—NF₂}⁺ Cl⁻,

[0060] —(CH₂)₃—NF—(CH₂)₂—{N[—CH₂—CH(OH)—CH₂—NMe₃]F}⁺ Cl⁻,

[0061]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃]F}²⁺2Cl⁻,

[0062] —(CH₂)₃—NF—(CH₂)₂—{N[—CH₂—CH(OH)—CH₂—NMe₃]₂}²⁺ 2Cl⁻,

[0063] —(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]₂—(CH₂)₂—NF₂}³⁺ 3Cl⁻,

[0064]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]F—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃]F}³⁺3Cl⁻,

[0065]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃]F₂}³⁺3Cl⁻,

[0066] —(CH₂)₃—NF—(CH₂)₂—{N[—CH₂—CH(OH)—CH₂—NMe₃]₂F}³⁺ 3Cl⁻,

[0067] —(CH₂)₃—NF—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃]₃}⁴⁺ 4Cl⁻,

[0068]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃]₂F}⁴⁺4Cl⁻,

[0069]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]₂—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃]F}⁴⁺4Cl⁻,

[0070]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]F—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃]₂}⁴⁺4Cl⁻,

[0071] where Me is methyl, and permutation of the examples mentioned forF results in a multiplicity of further, analogous examples. Someillustrative examples of R⁷ will now be exemplarily recited todemonstrate the range of the copolymers (Q). (Me=methyl):

[0072] —CH₂—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₅—C₄H₉]}⁺Cl⁻,

[0073]—CH₂—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₃H₆O)₂₀—(C₂H₄O)₂₀—C₄H₉]}⁺Cl⁻,

[0074] —CH₂—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH₂—C(O)—O—(C₂H₄O)₅—H]}⁺ Cl⁻,

[0075] —CH₂—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH₂—C(O)—O—(C₃H₆O)₁₆—CH₃]}⁺Cl⁻,

[0076]—CH₂—{N[—CH₂—CH(OH)—CH₂—NMe][—CH₂—CH₂—C(O)—O—(C₃H₆O)₂₀—C₂H₄O)₂₀—C(O)—CH═CH₂]}⁺Cl⁻,

[0077]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₅—CH₃]}⁺ Cl⁻,

[0078]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₃H₆O)₂₀—C₃H₅O]}⁺Cl⁻,

[0079]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₆—CH₂CH(OH)CH₂OH]}⁺Cl⁻,

[0080]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH₂—C(O)—O—(C₂H₄O)₂₅—C(O)CH₃]}⁺Cl⁻,

[0081] —(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH₂—C(O)—O—(C₃H₆O)₁₆—CH₃]}⁺Cl⁻,

[0082]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH₂—C(O)—O—(C₃H₆O)₂₀—(C₂H₄O)₂₀—C(O)—CH₂CH₂—NEt₂]}⁺Cl⁻,

[0083]—(CH₂)₃—NH—(CH₂)₂—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₅—C₄H₉]}⁺Cl⁻,

[0084]—(CH₂)₃—NH—(CH₂)₂—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₂—(C₃H₆O)₁₉—C₄H₉]}⁺Cl⁻,

[0085]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₁₁—C₄H₉]H}⁺Cl⁻,

[0086]—(CH₂)₃—N[—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₀—C₄H₉]—(CH₂)₂—{NH[—CH₂—CH(OH)—CH₂—NMe]}⁺Cl⁻,

[0087]—(CH)₃—NH—(CH)₂—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH₂—C(O)—O—(C₃H₆₀)₁₆—CH₃]}⁺Cl⁻,

[0088]—(CH)₃—NH—(CH)₂—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₃H₆O)₂—H]}⁺Cl⁻,

[0089]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₂—N[—CH₂—CH₂—C(O)—O—(C₂H₄O)₃₅—C(O)—CH═CH₂]H}⁺Cl⁻,

[0090] —(CH₂)₃—N[—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₄—C₄H₉]—(CH₂)₂—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₂—(C₃H₆O)₁₉—C₄H₉]}Cl⁻,

[0091]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₄—CH₃]}²⁺2Cl⁻,

[0092]—(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—(C₂H₄O)₅—C₄H₉]—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH₂—C(O)—O—(C₂H₄O)₁₅—(C₃H₆O)₅—CH₃}³⁺3Cl⁻,

[0093] —(CH₂)₃—{N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃][—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₁₁—C₄H₉][—CH₂—CH₂—C(O)—O—(C₂H₄O)₁₆—CH₃])}³⁺3Cl⁻,

[0094]—(CH₂)₃{N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃]₂[—CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₂—(C₃H₆O)₁₉—C₄H₉]}⁴⁺4Cl⁻,

[0095]—(CH₂)₃—{N[—CH₂—CH₂—C(O)—O—(C₂H₄O)₃₅—CH₃]—(CH₂)₂—N[—CH₂—CH(OH)—CH₂—NMe₃]₂[—CH₂—CH(OH)—CH₂—(C₂H₄O)₄—C₄H₉]}⁴⁺4Cl⁻.

[0096] Examples of A include hydrogen, the —OH group and also theradicals mentioned for R⁶ and R⁷.

[0097] Examples of B include

[0098] —SiMe₂—O—SiMe₂—,

[0099] —(SiMe₂O)₁₃—SiMe₂—,

[0100] —(SiMe₂O)₅₅—SiMe₂—,

[0101] —(SiMe₂O)₁₀₅—SiMe₂—,

[0102] —(SiMe₂O)₂₀₀—SiMe₂—,

[0103] —SiMe₂O—SiMeR⁷O—SiMe₂O—,

[0104] —(SiMe₂O)₇₀(SiMeR⁷O)₁—SiMe₂—,

[0105] —(SiMe₂O)₁₀₅(SiMeR⁷O)₂₀—SiMe₂—,

[0106] —(SiMe₂O)l₉₅(SiMeR⁷O)₁₅—SiMe₂—,

[0107] —(SiMe₂O)₂₃₀(SiMeR⁷O)₆—SiMe₂—,

[0108] —(SiMe₂O)₁₀₈(SiMeR⁷O)₂—SiMe₂—,

[0109] —(SiMe₂O)₁₃₉(SiMeR⁷O),—SiMe₂—,

[0110] —(SiMe₂O)₉—SiMe₃,

[0111] —(SiMe₂O)₅₉—SiMe₃,

[0112] —(SiMe₂O)₉₉—SiMe₃,

[0113] —(SiMe₂O)₁₃—SiMe₂—OCH₃,

[0114] —(SiMe₂O)₁₄—SiMe₂—OC₂H₄,

[0115] —(SiMe₂O)₄₄—SiMe₂—OC₃H₇,

[0116] —(SiMe₂O)₂₂—SiMe₂—OC₄H₉, and

[0117] —(SiMe₂O)₃₅—SiMe₂—OC₄H₉.

[0118] Examples of D include

[0119] —{CH₂ —N[—CH₂ —CH(OH)—CH₂ —NMe₃ ]-J-N[—CH₂ —CH(OH)—CH₂—NMe₃]—CH₂}—²⁺ 2Cl⁻,

[0120] —{CH₂—NH—J—N[—CH₂—CH(OH)—CH₂—NMe₃]—CH₂}—+Cl⁻,

[0121] —{CH₂—N[—CH₂—CH(OH)—CH₂—NMe₃]—J—NF—CH₂}—+Cl⁻,

[0122] —{CH₂—NH—J—NF—CH₂}—,

[0123] —{CH₂—NF—J—NF—CH₂}—,

[0124]—{(CH)₃—N[—CH₂—CH(OH)—CH₂—NMe₃]—J—N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₃}—-²⁺2Cl⁻,

[0125] —{(CH₂)₃—NH—J—N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₃ }—⁺ Cl⁻,

[0126] —{(CH₂)₃—N[—CH₂—CH(OH)—CH₂—NMe₃]—J—NF—(CH₂)₃}—⁺ Cl⁻,

[0127] —{(CH₂)₃—NH—J—NF—(CH₂)₃}—,

[0128] —{(CH₂)₃—NF—J—NF—(CH₂)₃}—,

[0129]—{CH₂—N[—CH₂—CH(OH)—CH₂—NMe₃]—J—N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₃}—²⁺ 2Cl⁻,

[0130] —{CH₂—N[—CH₂—CH(OH)—CH₂—NMe₃]—J—NH—(CH₂)₃}—²⁺ 2Cl⁻,

[0131] —{CH₂—NH—J—N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₃}—²⁺ 2Cl⁻,

[0132] —{CH₂—N[—CH₂—CH(OH)—CH₂—NMe₃]—J—NF—(CH₂)₃}—²⁺ 2Cl⁻,

[0133] —{CH₂—NF—J—N[—CH₂—CH(OH)—CH₂—NMe₃]—(CH₂)₃}—²⁺ 2Cl⁻,

[0134] —{CH₂—NF—J—NF—(CH₂)₃}—,

[0135] —{CH₂—NF—J—NH—(CH₂)₃}—,

[0136] —{CH₂—NH—J—NF—(CH₂)₃}—,

[0137] where Me represents methyl, and permutation of the cited exampleswith the radicals F and J results in a multiplicity of furtherillustrative structures.

[0138] Examples of E units include

[0139] —CH₂—CH(OH)—CH₂—NMe₃+Cl⁻, —CH₂—CH(OH)—CH₂—NMe₂Cl₂H₂₅+Cl⁻ and

[0140] —CH₂—CH(OH)—CH₂—NMe₂Cl₈H₃₇+Cl⁻.

[0141] Examples of F units are

[0142] —CH₂—CH₂—C(O)—O—(C₂H₄O)₆—H,

[0143] —CH₂—CH₂—C(O)—O—(C₂H₄O)₆—CH₃,

[0144] —CH₂—CH₂—C(O)—O—(C₂H₄O)₆—C(O)—CH ═CH₂,

[0145] —CH₂—CH₂—C(O)—O—(C₂H₄O)₆—C(O)—CH₂—CH₂—NEt₂,

[0146] —CH₂—CH₂—C(O)—O—(C₂H₄O)₆—C(O)—CH₂—CH₂—N(CH₂CH₂OH)₂,

[0147] —CH₂—CH₂—C(O)—O—(C₂H₄O)₆—C(O)CH₃,

[0148] —CH₂—CH₂—C(O)—O—(C₂H₄O)₁₄—H,

[0149] —CH₂—CH₂—C(O)—O—(C₂H₄O)₁₄—CH₃,

[0150] —CH₂—CH₂—C(O)—O—(C₂H₄O)₁₄—C(O)—CH═CH₂,

[0151] —CH₂—CH₂—C(O)—O—(C₂H₄O)₁₄—C(O)—CH₂—CH₂—NEt₂,

[0152] —CH₂—CH₂—C(O)—O—(C₂H₄O)₁₄—C(O)—CH₂—CH₂—N(CH₂CH₂OH)₂,

[0153] —CH₂—CH₂—C(O)—O—(C₂H₄O)₁₄—C(O)CH₃,

[0154] —CH₂—CH₂—C(O)—O—(C₂H₄O)₃₅—H,

[0155] —CH₂—CH₂—C(O)—O—(C₂H₄O)₃₅—CH₃,

[0156] —CH₂—CH₂—C(O)—O—(C₂H₄O)₃₅—C(O)—CH═CH₂,

[0157] —CH₂—CH₂—C(O)—O—(C₂H₄O)₃₅—C(O)—CH₂—CH₂—NEt₂,

[0158] —CH₂—CH₂—C(O)—O—(C₂H₄O)₃₅—C(O)—CH₂—CH₂—N(CH₂CH₂OH)₂,

[0159] —CH₂—CH₂—C(O)—O—(C₂H₄O)₃₅—C(O)CH₃,

[0160] —CH₂—CH₂—C(O)—O—(C₃H₆O)₆—H,

[0161] —CH₂—CH₂—C(O)—O—(C₃H₆O)₆—CH₃,

[0162] —CH₂—CH₂—C(O)—O—(C₃H₆O)₆—C(O)—CH═CH₂,

[0163] —CH₂—CH₂—C(O)—O—(C₃H₆O)₆—C(O)—CH₂—CH₂—NEt₂,

[0164] —CH₂—CH₂—C(O)—O—(C₃H₆O)₆—C(O)—CH₂—CH₂—N(CH₂CH₂OH)₂,

[0165] —CH₂—CH₂—C(O)—O—(C₃H₆O)₆—C(O)CH₃,

[0166] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₂—H,

[0167] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₂—CH₃,

[0168] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₂—C(O)—CH═CH₂,

[0169] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₂—C(O)—CH₂—CH₂—NEt₂,

[0170] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₂—C(O)—CH₂—CH₂—N(CH₂CH₂OH)₂,

[0171] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₂—C(O)CH₃,

[0172] —CH₂—CH₂—C(O)—O—(C₃H₆O)₃₅—H,

[0173] —CH₂—CH₂—C(O)—O—(C₃H₆O)₃₅—CH₃,

[0174] —CH₂—CH₂—C(O)—O—(C₃H₆O)₃₅—C(O)—CH═CH₂,

[0175] —CH₂—CH₂—C(O)—O—(C₃H₆O)₃₅—C(O)—CH₂—CH₂—NEt₂,

[0176] —CH₂—CH₂—C(O)—O—(C₃H₆O)₃₅—C(O)—CH₂—CH₂—N(CH₂CH₂OH)₂,

[0177] —CH₂—CH₂—C(O)—O—(C₃H₆O)₃₅—C(O)CH₃,

[0178] —CH₂—CH₂—C(O)—O—(C₃H₆O)₅—(C₂H₄O)₅—H,

[0179] —CH₂—CH₂—C(O)—O—(C₃H₆O)₅—(C₂H₄O)₅—CH₃,

[0180] —CH₂—CH₂—C(O)—O—(C₃H₆O)₅—(C₂H₄O)₅C(O)—CH═CH₂,

[0181] —CH₂—CH₂—C(O)—O—(C₃H₆O)₅—(C₂H₄O)₅C(O)—CH₂—CH₂—NEt₂,

[0182] —CH₂—CH₂—C(O)—O—(C₃H₆O)₅—(C₂H₄O)₅C(O)—CH₂—CH₂—N(CH₂CH₂OH)₂,

[0183] —CH₂—CH₂—C(O)—O—(C₃H₆O)₅—(C₂H₄₀)₅—C(O)CH₃,

[0184] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₀—(C₂H₄O)₁₀—H,

[0185] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₀—(C₂H₄O)₁₀—CH₃,

[0186] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₀—(C₂H₄O)₁₀C(O)—CH═CH₂,

[0187] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₀—(C₂H₄₀)₁₀C(O)—CH₂—CH₂—NEt₂,

[0188] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₀—(C₂H₄₀)₁₀C(O)—CH₂—CH₂—N(CH₂CH₂₀H)₂,

[0189] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₀—(C₂H₄₀)₁₀—C(O)CH₃,

[0190] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₄—C₄H₉

[0191] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₁₁—C₄H₉,

[0192] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₀—C₄H₉,

[0193] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₂(C₃H₆O)₉—C₄H₉,

[0194] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₄—C₃H₅O,

[0195] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₁₁—C₃H₅O,

[0196] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₀—C₃H₅O,

[0197] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₂(C₃H₆O) l₉—C₃H₅O,

[0198] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₄—CH₂—CH(OH)—CH₂—OH,

[0199] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₁₁—CH₂—CH(OH)—CH₂—OH,

[0200] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₀—CH₂—CH(OH)—CH₂—OH,

[0201] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₂(C₃H₆O)_(1,9)—CH₂—CH(OH)—CH₂—OH,

[0202] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₄—CH₂—CH(OH)—CH₂—NEt₂,

[0203] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₁ ₁—CH₂—CH(OH)—CH₂—NEt₂,

[0204] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₀—CH₂—CH(OH)—CH₂—NEt₂,

[0205] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₂(C₃H₆O)₁₉—CH₂—CH(OH)—CH₂—NEt₂,

[0206] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₄—CH₂—CH(OH)—CH₂—N(CH₂CH₂OH)₂,

[0207] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₁ ,—CH₂—CH(OH)—CH₂—N(CH₂CH₂OH)₂,

[0208] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₀—CH₂—CH(OH)—CH₂—N(CH₂CH₂OH)₂, and

[0209] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₂(C₃H₆O)₁₉—CH₂—CH(OH)—CH₂—N(CH₂CH₂OH)₂,

[0210] where Me is methyl and Et is ethyl.

[0211] Examples of J include

[0212] —CH₂—CH₂—C(O)—O—(C₂H₄O)₆—C(O)—CH₂—CH₂—,

[0213] —CH₂—CH₂—C(O)—O—(C₂H₄O)₁₄—C(O)—CH₂—CH₂—,

[0214] —CH₂—CH₂—C(O)—O—(C₂H₄O)₃₅—C(O)—CH₂—CH₂—,

[0215] —CH₂—CH₂—C(O)—O—(C₃H₆O)₆—C(O)—CH₂—CH₂—,

[0216] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₂—C(O)—CH₂—CH₂—,

[0217] —CH₂—CH₂—C(O)—O—(C₃H₆O)₃₅—C(O)—CH₂—CH₂—,

[0218] —CH₂—CH₂—C(O)—O—(C₃H₆O)₅—(C₂H₄O)₅—C(O)—CH₂—CH₂—,

[0219] —CH₂—CH₂—C(O)—O—(C₃H₆O)₁₀—(C₂H₄O)₁₀C(O)—CH₂—CH₂—,

[0220] —CH₂—CH₂—C(O)—O—(C₃H₆O)₅—(C₂H₄O)₁₅—C(O)—CH₂—CH₂—,

[0221] —CH₂—CH₂—C(O)—O—(C₃H₆O)₂₀—(C₂H₄O)₂₀—C(O)—CH₂—CH₂—,

[0222] —CH₂—CH₂—C(O)—NH—(C₃H₆O)₃—C₃H₆—NH—C(O)—CH₂—CH₂—,

[0223] —CH₂—CH₂—C(O)—NH—(C₃H₆O)₆—C₃H₆—NH—C(O)—CH₂—CH₂—,

[0224] —CH₂—CH₂—C(O)—NH—(C₃H₆O)₃₃—C₃H₆—NH—C(O)—CH₂—CH₂—,

[0225] —CH₂—CH₂—C(O)—NH—(C₃H₆O)₆₈—C₃H₆—NH—C(O)—CH₂—CH₂—,

[0226] —CH₂—CH₂—C(O)—NH—C₃H₆O—(C₂H₄O)₂—C₃H₆—NH—C(O)—CH₂—CH₂—,

[0227] —CH₂—CH₂—C(O)—NH—(C₃H₆O)₂—(C₂H₄O)₉—C₃H₆O—C₃H₆—NH—C(O)—CH₂—CH₂—,

[0228]—CH₂—CH₂—C(O)—NH—(C₃H₆O)₃—(C₂H₄O)₃₉—(C₃H₆O)₂—C₃H₆—NH—C(O)—CH₂—CH₂—,

[0229] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₄—CH₂—CH(OH)—CH₂—,

[0230] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₁₁—CH₂—CH(OH)—CH₂—,

[0231] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₀—CH₂—CH(OH)—CH₂—,

[0232] —CH₂—CH(OH)—CH₂—O—(C₂H₄O)₂₂(C₃H₆O)₁₉—CH₂—CH(OH)—CH₂—.

[0233] Examples of X⁻ anions which are suitable according to theinvention include chloride, bromide, hydrogensulfate, acetate, andsulfate ions and organic sulfonate ions, such astrifluoromethanesulfonate ion or p-toluenesulfonate ion. This list isexemplary and not limiting.

[0234] The invention further provides a process for preparing copolymers(Q) of the above general formula (I), which comprises reactingorganosilicon compounds or mixtures thereof that are selected fromcompounds of the general formulae (XI), (XII), (XIII), (XIV) and (XV)

H—NR¹—(R—NHR¹)_(g)—R—(SiR⁶ ₂O)₁—SIR⁶ ₂—R(—NHR¹—R)_(g)—NR¹—H  XI),

[0235] H—NR(—(R—NHR¹)_(g)—R—(SiR⁶₂)₁—{SiR¹[—R(—NHR¹—R)_(g)—NHR¹]—O}_(m)—R(—NHR¹—R)_(g)—NR¹—H  (XII),

R⁶ ₃SiO—(SiR⁶ ₂O)—{SiR⁶[—R(—NHR¹—R)_(g)—NHR¹]—O}_(m)—SIR⁶ ₃  (XIII),

MeO—SiR⁶ ₂O—(SiR⁶ ₂O)₁—{SiR⁶[—R(—NHR¹—R)_(g)—NHR¹]—O}_(m)—SiR⁶₂—OMe  (XIV),

H—NR¹—(R—NHR¹)_(g)—R—(SiR⁶ ₂O)—SiR⁶ ₂—R⁸  (XV),

[0236] with polyethers which are selected from compounds of the generalformulae (XVI) and (XVII)

CH₂═CH—C(O)—G—(R²—G)_(h)—[CH₂CH₂O]_(i)—[C₃H₆O]_(j)—[(CH₂)₄O]_(k)—(R²—G)_(h)—R⁵  (XVI),

[0237]

[0238] and organic compounds which are selected from compounds of thegeneral formulae (XVIII) and (XIX)

[0239] where Me is methyl and R¹, R², R³, R⁵, R⁶, G, X, g, h, i, j, k, land m are each as defined above.

[0240] The process can be carried out in bulk, solution or emulsion,stepwise or as a one-pot process. The organosilicon compounds used areknown and commercially available.

[0241] The cationic quat group is introduced in a different manner inthe present process than is customary according to the prior art. Thepresent process utilizes an aqueous reagent. Aqueous systems areinherently incompatible with hydrophobic siloxanes; modification ofsilicone oils using aqueous reagents is therefore customarily possibleonly with difficulties and to a poor yield. The present process,however, achieves excellent yields.

[0242] Examples of organosilicon compounds of the general formula (XI)which may be employed include

[0243] H₂N—CH₂—SiMe₂o—SiMe₂—CH₂—NH₂,

[0244] H₂N—CH₂—SiMe₂O—(SiMe₂O)₆—SiMe₂—CH₂—NH₂,

[0245] H₂N—CH₂—SiMe₂O—(SiMe₂O)₁ —SiMe₂—CH₂—NH₂,

[0246] H₂N—CH₂—SiMe₂O—(SiMe₂O)₉₈—SiMe₂—CH₂—NH₂,

[0247] H₂N—CH₂—SiMe₂o—(SiMe₂O)₁₅₀—SiMe₂—CH₂—NH₂,

[0248] H₂N—(CH₂)₃—SiMe₂o—SiMe₂—(CH₂)₃—NH₂,

[0249] H₂N—(CH₂)₃—SiMe₂O—(SiMe₂O)₆—SiMe₂—(CH₂)₃—NH₂,

[0250] H₂N—(CH₂)₃—SiMe₂O—(SiMe₂O)₁l—SiMe₂—(CH₂)₃—NH₂,

[0251] H₂N—(CH₂)₃—SiMe₂o—(SiMe₂O)₉₈—SiMe₂—(CH₂)₃—NH₂,

[0252] H₂N—(CH₂)₃—SiMe₂O—(SiMe₂O)₂₀₀—SiMe₂—(CH₂)₃—NH₂,

[0253] H₂N—(CH₂)₂—NH—(CH₂)₃—SiMe₂O—SiMe₂—(CH₂)₃—NH—(CH₂)₂—NH₂,

[0254] H₂N—(CH₂)₂—NH—(CH₂)₃—SiMe₂o—(SiMe₂O)₆—SiMe₂—(CH₂)₃—NH—(CH₂)₂—NH₂,

[0255]H₂N—(CH₂)₂—NH—(CH₂)₃—SiMe₂O—(SiMe₂O)l,—SiMe₂—(CH₂)₃—NH—(CH₂)₂—NH₂, and

[0256]H₂N—(CH₂)₂—NH—(CH₂)₃—SiMe₂o—(SiMe₂O)₅₅—SiMe₂—(CH₂)₃—NH—(CH₂)₂—NH₂—

[0257] Examples of organosilicon compounds of the general formula (XII)which may be employed include

[0258] H₂N—(CH₂)₃-SiMe₂O—{SiMe[(CH₂)₃—NH₂]O }—SiMe₂—(CH₂)₃—NH₂,

[0259]H₂N—(CH₂)₃—SiMe₂O—(SiMe₂O)₂₅—{SiMe[(CH₂)₃—NH₂]O}₅-SiMe₂—(CH₂)₃—NH₂,

[0260]H₂N—(CH₂)₃—SiMe₂O——(SiMe₂O)₅₀—{SiMe[(CH₂)₃—NH₂]O}₃—SiMe₂—(CH₂)₃—NH₂, and

[0261]H₂N—(CH₂)₃—SiMe₂O—(SiMe₂O)₇₀—{SiMe[(CH₂)₃—NH₂]O}₁—SiMe₂—(CH₂)₃—NH₂.

[0262] Examples of organosilicon compounds of the general formula (XIII)which may be employed include

[0263] Me₃SiO—(SiMe₂O)₂₅—{SiMe[(CH₂)₃—NH₂]O}SiMe₃,

[0264] Me₃SiO—(SiMe₂O)₄₅—{SiMe[(CH₂)₃—NH₂]O}₅SiMe₃,

[0265] Me₃SiO—(SiMe₂O)₁₀₀—{SiMe[(CH₂)₃—NH₂]O}₅SiMe₃,

[0266] Me₃SiO—(SiMe₂O)₁₃₀—{SiMe[(CH₂)₃—NH₂]O}₁SiMe₃,

[0267] Me₃SiO—(SiMe₂O)₁₀₅{SiMe[(CH₂)₃—NH—(CH₂)₂—NH₂]O}₂₀-SiMe₃l

[0268] Me₃SiO—(SiMe₂O)₁₉₅(SiMe[(CH₂)₃—NH—(CH₂)₂—NH₂]O)₁₅-SiMe₃,

[0269] Me₃SiO—(SiMe₂O)₂₃₀(SiMe[(CH₂)₃—NH—(CH₂)₂—NH₂]O)₆-SiMe₃,

[0270] Me₃SiO—(SiMe₂O)₁₀₈(SiMe[(CH₂)₃—NH—(CH₂)₂—NH₂]O)₂-SiMe₃, and

[0271] Me₃SiO—(SiMe₂O)₁₃₉(SiMe[(CH₂)₃—NH—(CH₂)₂—NH₂]O),-SiMe₃.

[0272] Examples of organosilicon compounds of the general formula (XIV)which may be employed include

[0273] Me₃SiO—(SiMe₂O)₂₅—{SiMe[(CH₂)₃—NH₂]O}₅SiMe₃,

[0274] Me₃SiO—(SiMe₂O)₄₅—{SiMe[(CH₂)₃—NH₂]O}₅SiMe₃,

[0275] Me₃SiO—(SiMe₂O)₁₀₀—{SiMe[(CH₂)₃—NH₂]O}₅SiMe₃,

[0276] Me₃SiO—(SiMe₂O)₁₃₀—{SiMe[(CH₂)₃—NH₂]O},SiMe₃,

[0277] MeOSiMe₂O—(SiMe₂O)₄₀{SiMe[(CH₂)₃—NH—(CH₂)₂—NH₂]O}₁—SiMe₂OMe,

[0278] MeOSiMe₂O—(SiMe₂O)₇₀{SiMe[(CH₂)₃—NH—(CH₂)₂—NH₂]O}₁—SiMe₂OMe,

[0279] MeOSiMe₂O—(SiMe₂O)₂₀₀{SiMe[(CH₂)₃—NH—(CH₂)₂—NH₂]O}₁—SiMe₂OMe.

[0280] Examples of employed organosilicon compounds of the generalformula (XV) are

[0281] H₂N—CH₂—(SiMe₂O)₁₃—SiMe₂—OCH₃,

[0282] H₂N—CH₂—(SiMe₂O)l₄—SiMe₂—OC₂H₄,

[0283] H₂N—CH₂—(SiMe₂O)₄₄—SiMe₂—OC₃H₇,

[0284] H₂N—CH₂—(SiMe₂O)₂₂—SiMe₂—OC₄H₉,

[0285] H₂N—CH₂—(SiMe₂O)₃₅—SiMe₂—OC₄H₉.

[0286] H₂N—(CH₂)₃—(SiMe₂O)₉—SiMe₃,

[0287] H₂N—(CH₂)₃—(SiMe₂O)₅₉—SiMe₃,

[0288] H₂N—(CH₂)₃—(SiMe₂O)₉₉—SiMe₃,

[0289] H₂N—(CH₂)₃—(SiMe₂O)₁₃—SiMe₂—OCH₃,

[0290] H₂N—(CH₂)₃—(SiMe₂O)l₄—SiMe₂—OC₂H₄,

[0291] H₂N—(CH₂)₃—(SiMe₂O)₄₄—SiMe₂—OC₃H₇,

[0292] H₂N—(CH₂)₃—(SiMe₂O)₂₂—SiMe₂—OC₄H₉,

[0293] H₂N—(CH₂)₃—(SiMe₂O)₃₅—SiMe₂—OC₄H₉.

[0294] H₂N—(CH₂)₂—NH—(CH₂)₃—(SiMe₂O)₇—SiMe₃,

[0295] H₂N—(CH₂)₂—NH—(CH₂)₃—(SiMe₂O)₁₂—SiMe₃,

[0296] with organosilicon compounds of the general formulae (XI), (XII),(XIII) and (XV) being preferred, especially organosilicon compounds ofthe general formulae (XI), (XIII) and (XV).

[0297] Examples of employed polyethers of the general formulae (XVI) and(XVII), which are likewise commercially available (for example from CrayValley, Siber Hegner AG, NOF Corp.) or are preparable by methods knownto one skilled in the art, are

[0298] CH₂═CH—C(O)—O—(C₂H₄O)₆—H,

[0299] CH₂═CH—C(O)—O—(C₂H₄O)₁₄—H,

[0300] CH₂═CH—C(O)—O—(C₂H₄O)₃₅—H,

[0301] CH₂═CH—C(O)—O—(C₃H₆O)₆—H,

[0302] CH₂═CH—C(O)—O—(C₃H₆O)₁₂—H,

[0303] CH₂═CH—C(O)—O—(C₃H₆O)₃₅—H,

[0304] CH₂═CH—C(O)—O—(C₂H₄O)₃—(C₃H₆O)₃—H,

[0305] CH₂═CH—C(O)—O—(C₂H₄O)₅—(C₃H₆O)₅—H,

[0306] CH₂═CH—C(O)—O—(C₂H₄O)₁₀—(C₃H₆O)₁₀—H,

[0307] CH₂═CH—C(O)—O—(C₂H₄O)₆—CH₃,

[0308] CH₂═CH—C(O)—O—(C₂H₄O)₁₆—CH₃,

[0309] CH₂═CH—C(O)—O—(C₂H₄O)₂₄—CH₃,

[0310] CH₂═CH—C(O)—O—(C₂H₄O)₂₅—CH₃,

[0311] CH₂═CH—C(O)—O—(C₃H₆O)₆—CH₃,

[0312] CH₂═CH—C(O)—O—(C₃H₆O)₁₂—CH₃,

[0313] CH₂═CH—C(O)—O—(C₃H₆O)₃₅—CH₃,

[0314] CH₂═CH—C(O)—O—(C₂H₄O)₃—(C₃H₆O)₃—CH₃,

[0315] CH₂═CH—C(O)—O—(C₂H₄O)₅—(C₃H₆O)₅—CH₃,

[0316] CH₂═CH—C(O)—O—(C₂H₄O)₁₀—(C₃H₆O)₁₀—CH₃,

[0317] CH₂═CH—C(O)—O—(C₂H₄O)₃—C(O)—CH═CH₂,

[0318] CH₂═CH—C(O)—O—(C₂H₄O)₆—C(O)—CH═CH₂,

[0319] CH₂═CH—C(O)—O—(C₂H₄O)₁₄—C(O)—CH═CH₂,

[0320] CH₂═CH—C(O)—O—(C₂H₄O)₃₅—C(O)—CH═CH₂,

[0321] CH₂═CH—C(O)—O—(C₃H₆O)₃—C(O)—CH═CH₂,

[0322] CH₂═CH—C(O)—O—(C₃H₆O)₆—C(O)—CH═CH₂,

[0323] CH₂═CH—C(O)—O—(C₃H₆O)₁₂—C(O)—CH═CH₂,

[0324] CH₂═CH—C(O)—O—(C₃H₆O)₃₅—C(O)—CH═CH₂,

[0325] CH₂═CH—C(O)—O—(C₂H₄O)₃—(C₃H₆O)₃—C(O)—CH═CH₂,

[0326] CH₂═CH—C(O)—O—(C₂H₄O)₅—(C₃H₆O)₅—C(O)—CH═CH₂,

[0327] CH₂═CH—C(O)—O—(C₂H₄O)₁₀—(C₃H₆O)₁₀—C(O)—CH═CH₂,

[0328] Examples of organic compounds of the general formulae (XVIII) and(XIX), which may be employed and which are likewise commerciallyavailable (for example from Degussa AG), include

[0329] It is preferable to use at least 0.001 mol, more preferably atleast 0.1 mol, yet more preferably at least 0.5, and preferably at most1.75 mol of polyether of the general formulae (XVI) and (XVII) and alsopreferably at least 0.001 mol, more preferably at least 0.1 mol, yetmore preferably at least 0.5, and preferably at most 1.75 mol of organiccompound of the general formulae (XVIII) and (XIX) in the process, permole of amine group of the organosilicon compound of the generalformulae (XI), (XII), (XIII), (XIV) and (XV).

[0330] When the process utilizes difunctional polyether compounds of thegeneral formulae (XVI) and (XVII) and the fractions of polyethercompound of the general formulae (XVI) and (XVII) and of the organiccompound of the general formulae (XVIII) and (XIX) are chosen such thatexcess acrylate and epoxy radicals appear in the copolymers of thegeneral formula (I), these reactive end groups may subsequentlycrosslink or be specifically crosslinked.

[0331] The products of the general formula (I) having reactive acrylateand epoxy end groups can be rendered stable in storage for severalmonths against free-radical crosslinking in daylight by means of thecustomary free-radical inhibitors such as hydroquinone monomethyl etheror phenothiazine. Stabilization against possible postcrosslinking due toprimary or secondary amine groups which remain in the product with theacrylate or epoxy end groups can be achieved by amidating these aminegroups with organic acid anhydrides or acyl chlorides, or by aMichael-type reaction to saturate the amine groups with monomericacrylic ester compounds after the actual reaction has taken place.Remaining primary or secondary amine groups in the copolymers of thegeneral formula (I) may in addition also be protonated, alkylated orquaternized; this also applies to tertiary amine groups. The process forpreparing the copolymers of the general formula (I) may utilizecompounds known from the literature which catalyze Michael-typereactions and epoxy ring opening reactions. Examples are Bronsted acidssuch as phosphoric acid, sulfuric acid, hydrochloric acid, glacialacetic acid, propionic acid and formic acid, or their aqueous solutions;Lewis acids such as lithium perchlorate, zinc tetrafluoroborate,iron(II) chloride and tin(IV) chloride, and Brønsted bases, for examplesodium methoxide and alkali metal amides, and also ammonium chloride,tetraalkylammonium bromides and alkali metal iodides.

[0332] The process may additionally employ organic solvents, water, ormixtures thereof, the abovementioned polyethers of the general formulae(XVI) and (XVII) and also the reaction product itself also potentiallyserving as a solvent. Examples of organic solvents are toluene, xylene,THF, n-butyl acetate, isopropanol, butanol and dimethoxyethane. Organicsolvent used is preferably removed again after the reaction or afterfollow-up reactions.

[0333] When the process is carried out in emulsion, emulsifiers orsurface-active agents may correspondingly be present. Similarly, whenthe process is carried out in emulsion, the reaction product itself mayby virtue of its surface-active properties be used as an emulsifier orcoemulsifier.

[0334] The copolymers of the general formula (I) can be equilibratedwith organopolysiloxanes selected from the group consisting of linearorganopolysiloxanes having terminal triorganosiloxy groups,organopolysiloxanes having linear, terminal hydroxyl groups, cyclicorganopolysiloxanes and interpolymers of diorganosiloxane andmonoorganosiloxane units.

[0335] As linear organopolysiloxanes having terminal triorganosiloxygroups it is preferable to use those of the general formula (XX)

R⁶ ₃SiO(SiR⁶ ₂O)_(q)SiR⁶ ₃  (XX),

[0336] as linear organopolysiloxanes having terminal hydroxyl groups itis preferable to use those of the general formula (XXI)

HO(SiR⁶ ₂O)_(r)H  (XXI),

[0337] as cyclic organopolysiloxanes it is preferable to use those ofthe general formula (XXII)

(R⁶ ₂SiO)_(s)  (XXII)

[0338] and as interpolymers it is preferable to use those composed ofunits of the general formulae (XXIII), (XXIV) and (XXV)

R⁶ ₃SiO_(1/2), R⁶ ₂SiO and R⁶SiO_(3/2)  (XXIII, XXIV, XXV),

[0339] where

[0340] q and r are each 0 or an integer from 1 to 1500,

[0341] s is an integer from 3 to 12, and R⁶ is as defined above.

[0342] The quantitative ratios of the organopolysiloxanes of the generalformulae (XX) to (XXV) that are used in the optionally conductedequilibration and of the copolymers of the general formula (I) aremerely determined by the fraction of polyether and/or quat groups whichis desired in the copolymers produced in the optionally conductedequilibration and by the average chain length desired for the siloxaneunits.

[0343] The optionally conducted equilibration utilizes acidic catalysts,or preferably, basic catalysts, to further the equilibration. Examplesof preferable acidic catalysts include sulfuric acid, phosphoric acid,trifluoromethanesulfonic acid, phosphorus nitride chlorides and acidiccatalysts which are solid under the reaction conditions, such asacid-activated bleaching earth, acidic zeolites, sulfonated carbon andsulfonated styrene-divinylbenzene interpolymer, with phosphorus nitridechlorides being preferred as acidic catalysts. Acidic catalysts arepreferably used in amounts from 5 to 1000 weight ppm (parts permillion), more preferably 50 to 200 weight ppm, all based on the totalweight of the organosilicon compounds used. Examples of basic catalystsinclude benzyltrimethylammonium hydroxide, tetramethylammoniumhydroxide, alkali metal hydroxides, alkaline earth metal hydroxides inmethanolic solution, phosphonium hydroxides, and silanolates. Preferenceis given to ammonium hydroxides, which are used in amounts from 50 to10,000 weight ppm more preferably 500 to 2000 weight ppm, all based onthe total weight of the organosilicon compounds used.

[0344] The optionally conducted equilibration is preferably conducted at80 to 150° C. and at the pressure of the surrounding atmosphere, i.e.,between 900 and 1100 hPa. If desired, however, higher or lower pressurescan be employed as well. The equilibrating can be conducted inwater-immiscible solvents, such as toluene. When solvents are used, theamounts employed are preferably 5 to 20 weight percent, based on thetotal weight of the particular organosilicon compounds used. Thecatalyst can be rendered inactive before the as-equilibrated mixture isworked up.

[0345] Advantages of the process for preparing the copolymers of thegeneral formula (I) are the simple implementation in the form of aone-pot synthesis and the use of starting materials which are simple andcommercially available in a large variety. The process has the furtheradvantage that, first, the properties of the copolymers are easilyvaried through the choice of reactants, and second, to a certain extent,the stoichiometry of the reactants can be used with otherwise virtuallyunchanged reaction parameters to vary not only the viscosity but tosimply vary also the hydrophilicity, the amine number, and the nature ofthe end groups of the products, as well as the ratio of the siloxane topolyether and/or quat units.

[0346] The copolymers (Q) of the general formula (I) are notable fortransparency, low discoloration, hydrolysis resistance and transitionmetal absence. Owing to their cationogenicity, which is due to thenumber of quaternary amino groups in the molecule, the copolymers of theinvention possess very good adhesion to substrates such as textiles orpaper and are notable for their hydrophilicity, which is comparativelyhigh for organosilicon compounds.

[0347] The copolymers (Q) are therefore useful, for example, asingredients of emulsions, in solution or in solvent-free compositionsfor the treatment of textile sheet materials, for example wovens, knitsor nonwovens, textile fiber and yarn finishing and modification and alsoleather and paper treatment. Finishing or modifying with the appropriatecopolymers (Q) can be used to confer desired properties such as forexample a soft, supple hand, improved elasticity, antistatic properties,modified coefficients of friction, surface smoothness, luster, creaserecovery, color fastnesses, durability to laundering, hydrophilicity,tear strength, reduced tendency to pill, easy care and soil releaseproperties and also improved wear comfort. The effects achieved throughfinishing with the copolymers (Q) exhibit good to very good durabilityto washing and reconditioning operations, depending on the structure ofthe copolymer (Q), on the structure of the substrate and on the washconditions. The finishing or modification of textile sheet materials,fibers, yarns, paper and leather with the copolymers (Q) can further beused to improve the industrial processibility, for example theprocessing and manufacturing speed, and also the quality of thematerials.

[0348] The textile sheet materials fibers and yarns may have beenfabricated from mineral fibers, such as glass fibers or silicate fibers,natural fibers such as for example wool, silk or cotton, manufacturedfibers, such as for example polyester or polyamide fibers, cellulosefibers, interpolymer fibers or metal fibers. Filament fibers or staplefibers composed of the substrates mentioned can likewise be used. It isfurther possible to use sheet materials composed of fiber blends, suchas cotton/polyester, paper and also natural sheet materials such asleather.

[0349] The coating or finish can be applied in the knife coatingprocess, dip (squeeze) process, extrusion process, spraying flocking oratomizing process, padding, exhaust or dip-whiz processes. Similarly,all varieties of roller coatings, such as gravure roll, kiss roll, orapplication via multiroll systems, and also printing, for example(rotary) screen printing, are possible. Finishing or coating can furtherbe carried out by foam application and subsequent calendering, using acalender, including a hotmelt calender.

[0350] The copolymers (Q) can further be used as additives in coatingsand paints. Additions of the copolymers (Q) to, for example, radiation-or addition-curing paints lead to a reduction in the surface roughnessand thus to a reduction in the slip resistance of the paint. Thecopolymers (Q) can further serve as ingredients in cosmeticformulations, for example as conditioners in hair shampoos, and asbuilding protectants. In addition, the copolymers (Q) constitutesurface-active agents and can be used as detergents, surfactants,emulsifiers, defoamers and foam stabilizers.

[0351] All the above symbols in the above formulae each have theirmeanings independently of each other. The silicon atom is tetravalent inall the formulae. Where a hydrocarbyl group may be interrupted by aheteroatom or heteroatom-containing group, may be substituted, or maycontain enumerated organic groups, these modifications of thehydrocarbyl group are not exclusive, and a given hydrocarbyl group maycontain none, all, or any combination of these modifications, unlessotherwise indicated.

EXAMPLES

[0352] In the examples which follow, all parts and percentages are byweight, unless otherwise stated. Also, unless otherwise stated, theexamples are carried out at the pressure of the surrounding atmosphere,i.e., at about 1000 hPa, and at room temperature, i.e., at about 20° C.or at a temperature which results without additional heating and coolingwhen the reactants are added together at room temperature. Allviscosities reported in the examples relate to a temperature of 25° C.AN is the amine number, the amine number being the number of ml of 1NHCl which is needed to neutralize 1 g of substance.

Example 1

[0353]250 g of a terminally aminopropyl-functional silicone oil(AN=0.18) are stirred at 50° C. for 12 h with 4.85 g of a 70% aqueoussolution of 2,3-epoxypropyltrimethylammonium chloride (QUAB® 151,Degussa AG) in 4 g of i-propanol. Subsequently, 25.69 g of anα-acrylate- and ω-methoxy-functionalized oligoethylene glycol (MW =ca.1142) in 250 g of i-propanol are added and stirred in under refluxconditions for 2 h. Removal of the solvent under reduced pressure leaves279 g of a colorless tallowy solid (AN=0.16).

Example 2

[0354]250 g of a terminally aminopropyl-functional silicone oil(AN=0.26) are stirred at 50° C. for 12 h with 14.02 of a 70% aqueoussolution of 2,3-epoxypropyltrimethylammonium chloride (QUAB® 151,Degussa AG) in 10 g of i-propanol. 143 g of an α-glycidoxy- andω-butoxy-functionalized polyethylene glycol-polypropylene glycolcopolymer (MW=ca. 2200; about 22 EO units and 19 PO units) in 250 g ofi-propanol are added and stirred in under reflux conditions for afurther 6 h. Removal of the solvent under reduced pressure leaves 302.5g of a colorless solid (AN=0.21).

Example 3

[0355]250 g of a terminally aminopropyl-functional silicone oil(AN=0.56) are stirred at 50° C. for 12 h with 15.1 g of a 70% aqueoussolution of 2,3-epoxypropyltrimethylammonium chloride (QUABO 151,Degussa AG) in 10.6 g of i-propanol. Subsequently, 67 g of anα-glycidoxy- and ω-butoxy-functionalized polyethylene glycol (MW=ca.319) in 250 g of i-propanol are added and stirred in under refluxconditions for a further 6 h. Removal of the solvent under reducedpressure leaves 327.5 g of a white waxy solid (AN=0.42).

Example 4

[0356]250 g of an a-aminopropyl- and w-i-butoxy-functional silicone oil(AN=0.5) are stirred at 50° C. for 12 h with 27 g of a 70% aqueoussolution of 2,3-epoxypropyltrimethylammonium chloride (QUAB® 151,Degussa AG) in 19 g of i-propanol. Subsequently, 142.75 g of anα-acrylate- and 8,51-methoxy-functionalized oligoethylene glycol (MW=ca.1142) in 250 g of i-propanol are added and stirred in under refluxconditions for 4 h. Removal of the solvent under reduced pressure leaves412 g of a slightly yellowish solid (AN=0.30).

Example 5

[0357]250 g of an aminoethylaminopropyl-functionalized silicone oilhaving trimethylsilyl end groups (AN=0.25) are stirred at 50° C. for 12h with 13.48 g of a 70% aqueous solution of2,3-epoxypropyltrimethylammonium chloride (QUAB® 151, Degussa AG) in 9.5g of i-propanol. Subsequently, 25.2 g of an α-acrylate- andω-methoxy-functionalized oligoethylene glycol (MW=ca. 807) in 250 g ofi-propanol are added and stirred in under reflux conditions for 3 h.Removal of the solvent under reduced pressure leaves 284.5 g of aslightly yellowish solid (AN=0.22).

Example 6

[0358]250 g of an aminoethylaniinopropyl-functionalized silicone oilhaving trimethylsilyl end groups (AN=0.60) are stirred at 70° C. for 12h with 64.13 g of an aqueous solution of2,3-epoxypropyldimethyldodecylammonium chloride (QUAB® 342, Degussa AG)and 4.35 g of KOH in 100 g of ethanol. Subsequently, 75.8 g of anα-glycidoxy- and ω-butoxy-functionalized polyethylene glycol (MW=ca.1010) and 150 g of i-propanol are added and stirred in under refluxconditions for a further 8 h. Removal of the solvent under reducedpressure leaves 351 g of a white waxy solid (AN=0.43).

Example 7

[0359]250 g of a terminally aminopropyl-functional silicone oil(AN=0.18) are stirred at 50° C. for 12 h with 9.7 g of a 70% aqueoussolution of 2,3-epoxypropyltrimethylammonium chloride (QUAB® 151,Degussa AG) in 7 g of i-propanol. Subsequently, 12.45 g of anα,ω-diacrylate-functionalized oligoethylene glycol (MW=ca. 830) and 34.2g of an α-acrylate- and ω-methoxy-functionalized oligoethylene glycol(MW=ca. 1142) in 250 g of i-propanol are added and stirred in underreflux conditions for 4 h. Removal of the solvent under reduced pressureleaves 303 g of a slightly yellowish tallowy solid (AN 0.15).

Example 8

[0360]250 g of a terminally aminopropyl-functional silicone oil(AN=0.18) are stirred at 50° C. for 12 h with 9.7 g of a 70% aqueoussolution of 2,3-epoxypropyltrimethylammonium chloride (QUAB® 151,Degussa AG) in 7 g of i-propanol. Subsequently, 38 g of anα,ω-diacrylate-functionalized oligoethylene glycol (MW=ca. 1126) in 250g of i-propanol are added and stirred in under reflux conditions for 2h. Removal of the solvent under reduced pressure leaves 295 g of aslightly yellowish tallowy solid (AN=0.15).

Performance Examples

[0361] Padding Process:

[0362] A bleached, unfinished PES/CO 65/35 twill fabric having a basisweight of 200 g/m² was used. The reference used was a finish with astandard silicone softener emulsion (microemulsion of anamino-functional polydimethylsilokane) and also fabric padded with waterand dried.

[0363] The fabric was saturated with the respective liquor, squeezed offto 70% wet pickup on a two-bowl pad-mangle, tentered and dried in aMathis laboratory tenter at 150° C. for 2 min. The fabric was thenconditioned at 23° C. and a relative humidity of 50% for at least 12hours.

[0364] Determination methods for the results of the performanceexamples:

[0365] A) Determination of Soft Hand (Hand Assessment)

[0366] Since the soft hand of textiles is greatly dependent on thesubjective feel of the tester, only the boundary conditions can bestandardized and not the assessment itself. To ensure reproducibilitynonetheless, the finished samples were assessed and ranked in order withregard to their soft hand. To this end, 10 testers awarded 1 to n pointsto n tested samples, n points being awarded to the softest sample and 1point to the least soft sample. The reported result is accordingly theaverage value of points scored by each sample.

[0367] B) Determination of Droplet Absorption Time

[0368] After finishing, the finished sample was conditioned at 23° C.and 50% relative humidity for eight hours before a droplet of deionizedwater was placed on the tensioned fabric surface from a height of 6 cmand the time taken for the droplet of water to be absorbed by the fabricwas determined, 3 minutes being the longest time allowed. Fivedeterminations were carried out and the results averaged.

[0369] Table 1 summarizes for some performance examples the results ofthe fabric finished by means of the padding process. TABLE 1 ExamplesEmulsion of 9 10 11 12 13 14 15 16 C1 C2 Example 1 20 g/l Example 2 20g/l Example 3 20 g/l Example 4 20 g/l Example 5  20 g/l Example 6 20 g/lExample 7 20 g/l Example 8 20 g/l Standard Si  20 g/l microemulsionGlacial  0.5 g/l  0.5 g/l  0.5 g/l  0.5 g/l  0.5 g/l  0.5 g/l  0.5 g/l 0.5 g/l   0.5 g/l  0.5 g/l acetic acid Droplet absorption 16 <1 <1 <1130 54  8 13 >180 108 time (seconds) Hand  7.1  2.1  3.6  1.9  6.3  3.8 7.9  8.7   3.6  0

[0370] While embodiments of the invention have been illustrated anddescribed, it is not intended that these embodiments illustrate anddescribe all possible forms of the invention. Rather, the words used inthe specification are words of description rather than limitation, andit is understood that various changes may be made without departing fromthe spirit and scope of the invention.

What is claimed is:
 1. A copolymer (Q) of the general formula (I) A-B-(D-B)_(o)-A  (I), where A is an —R¹ or —OR¹ radical or a monovalent radical of the general formula (II), —R—[(NH_(a) _(b)F_(c))^((a+2b+c−1)+)—R]_(g)—(NH_(d)E_(e)F_(f))^((d+2e+f−2)+)[_(g)(a+2b+c−1)+d+2e+f−2]X⁻  (II), R¹ is a hydrogen atom or a monovalent hydrocarbyl radical having 1 to 100 carbon atoms optionally interrupted by and/or substituted by one or more of N, O, P, B, Si, or S, optionally containing one or more of —C(O)—, —C(O)O—, —C(O)NR⁹—, —NR⁹—, —O—, —S—, ═N—, or ≡N units, and optionally substituted by one or more —NR⁹—, —OH, or —SH groups, R is a divalent hydrocarbyl radical having 1 to 50 carbon atoms optionally interrupted by and optionally substituted by one or more of N, O, P, B, Si, S and which optionally contains one or more —C(O)—, —C(O)O—, —C(O)NR⁹—, —NR⁹—, —O—, —S—, or ═N— units, R⁹ is a hydrogen atom or a monovalent hydrocarbyl radical having 1 to 18 carbon atoms optionally interrupted by one or more of N, O, P, B, Si, S, and optionally substituted by one or more of —OH, or —SH groups, a, b and c are integers from 0 to 2 subject to the condition that the sum of a+b+c is 1 or 2, d, e and f are integers from 0 to 3 subject to the condition that the sum of d+e+f is 2 or 3, g is an integer from 0 to 10, E is a radical of the general formula (III) —R²—NR³ ₃+  (III), R² is a divalent hydrocarbyl radical having 1 to 10 carbon atoms optionally interrupted by and optionally substituted by one or more of N, O, P, B, Si, or S, and optionally containing one or more of —C(O)—, —C(O)O—, —C(O)NR⁹—, —NR⁹—, —O—, —S—, ═N—, or ≡N units, and optionally substituted by one or more of —NR⁹—, —OH, or —SH groups, R³ is a monovalent hydrocarbyl radical having 1 to 20 carbon atoms optionally interrupted by and optionally substituted by one or more of N, O, P, B, Si, or S, optionally containing one or more of —C(O)—, —C(O)O—, —C(O)NR⁹—, —NR₉—, —O—, —S—, ═N—, or ≡N units, and substituted by one or more of —NR⁹—, —OH, and/or —SH groups, X⁻ is an organic or inorganic anion, F is a radical of the general formulae (IV) or (V) —CH₂—CHR⁴—C(O)—G—(R²—G)_(h)—[CH₂CH₂O]_(i)—[C₃H₆O]_(j)—[(CH₂)₄O]_(k)—(R²—G)_(h)—R⁵  (IV),—CH₂—CH(OH)—CH₂—G—(R²—G)_(h)—[CH₂CH₂O]_(i)—[C₃H₆O]_(j)—[(CH₂)₄O]_(k)—(R²—G)_(h)—R⁵  (V), R⁴ is a hydrogen atom or methyl radical, R⁵ is a hydrogen atom, a monovalent branched or unbranched hydrocarbyl radical having 1 to 10 carbon atoms or a unit selected from the group consisting of CH₂═CR⁴—C(O)—, (R¹)₂N—CH₂—CHR⁴—C(O)—, R⁴—CH₂—C(O)—, HO—CH₂—CH(OH)—CH₂— and

G is a divalent group —O— or —NR⁹—, h is 0 or 1, i, j and k are each an integer from 0 to 200, B is a divalent radical comprising one or more units which are selected from the general formulae (VIa), (VIb), (VIc), (VId) and A (SiR⁶ ₂O_(2/2))₁ (VIa), (SiR⁶R⁷O_(2/2))_(m)  (VIb),(—SiR⁶ ₂—)_(p+1) (VIc), (SiO_(3/2))_(p)  (VId), R⁶ is a hydrogen atom, —OR¹, or a monovalent alkyl radical having 1 to 200 carbon atoms optionally substituted by one or more of halogen atoms, carboxyl groups, epoxy groups, hydroxyl groups or polyether groups, and optionally interrupted by one or more of the units —C(O)—, —C(O)O—, —C(O)NR⁹—, —NR⁹—, —O—, or —S—, R⁷ is a monovalent radical of the general formula (II), l and m are each an integer from 0 to 5000, p is an integer from 0 to 500, D is a divalent radical of the general formula (VIII), —{[R—(NH_(a)E_(b)F_(c))]_(n)—J—[(NH_(a)E_(b)F_(c))—R]_(n)}^([2n(a+2b+c)−4]+)[2n(a+2b+c)−4]X⁻  (VIII), n is an integer from 1 to 10, J is a divalent radical of the general formulae (IX) or (X), —CH₂—CHR⁴—C(O)—G—(R⁴—G)_(h)—[CH₂CH₂O]_(i)—[C₃H₆O]_(j)—[(CH₂)₄O]_(k)—(R²—G)_(h)—C(O)—CHR⁴—CH₂—  (IX),—CH₂—CH(OH)—CH₂—G—(R²—G)_(h)—[CH₂CH₂O]_(i)[C₃H₆]_(j)—[(CH₂)₄O]_(k)—(R²—G)h—CH₂—CH(OH)—CH₂—  (X), o is an integer ≧0, with the proviso that the copolymers of the general formula (I) contain at least one E radical and one F radical.
 2. The copolymer (Q) of claim 1 having an average molecular weight M_(n) from 500 g/mol to 1,000,000 g/mol.
 3. The copolymer (Q) of claim 1, wherein R is a —(CH₂)—, —(CH₂)₂— or —(CH₂)₃—radical.
 4. The copolymer (Q) of claim 1, wherein R¹ is hydrogen, methyl, ethyl, propyl, cyclohexyl or acetyl.
 5. The copolymer (Q) of claim 1, wherein R² is a linear or branched alkylene radical.
 6. A process for preparing a copolymer (Q) of claim 1, comprising reacting organosilicon compounds or mixtures thereof that are selected from compounds of the general formulae (XI), (XII), (XIII), (XIV) and (XV) H—NR¹—(R—NHR¹)_(g)—R—(SiR⁶ ₂O)₁—SiR⁶ ₂—R(—NHR¹—R)_(g)—NR¹—H  (XI),H—NR¹—(R—NHR¹)_(g)—R—(SiR⁶ ₂O)_(g)—{SiR⁶[—R(—NHR¹—R)_(g)—NHR¹]—O}_(m)—R(—NHR¹—R)_(g)—NR¹—H  (XII),R⁶ ₃SiO—(SiR⁶ ₂O)₁—{SiR⁶[—R(—NHR¹—R)_(g)NHR¹]—O}_(m)—SR⁶ ₃  (XIII),MeO—SiR⁶ ₂O—(SiR⁶ ₂O)—{SiR⁶[—R(—NHR¹—R)_(g)—NHR¹]—O}_(m)—SiR⁶ ₂—OMe  (XIV),H—NR¹—(R—NHR¹)_(g)—R—(SiR⁶ ₂O)_(l)—SiR⁶ ₂—R⁸  (XV), with polyethers which are selected from compounds of the general formulae (XVI) and (XVII) CH₂═CH—C(O)—G—(R²—G)_(h)—[CH₂CH₂O]_(j)—[C₃H₆O]_(j)—[(CH₂)₄O ]_(k)—(R²—G)_(h)—R⁵  (XVI),

and organic compounds which are selected from compounds of the general formulae (XVIII) and (XIX)

where Me is methyl. 